JP2832758B2 - Method for producing a copper-plated steel sheet for multi-turn pipe - Google Patents

Method for producing a copper-plated steel sheet for multi-turn pipe

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JP2832758B2
JP2832758B2 JP4265191A JP4265191A JP2832758B2 JP 2832758 B2 JP2832758 B2 JP 2832758B2 JP 4265191 A JP4265191 A JP 4265191A JP 4265191 A JP4265191 A JP 4265191A JP 2832758 B2 JP2832758 B2 JP 2832758B2
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copper
steel sheet
pyrophosphate
plating
multi
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JPH06108284A (en
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幸夫 内田
政義 多々納
佳久 家口
栄次 渡辺
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日新製鋼株式会社
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【発明の詳細な説明】 DETAILED DESCRIPTION OF THE INVENTION

【001】 [001]

【産業上の利用分野】本発明は、自動車のブレ−キチュ−ブ、冷蔵庫の放冷管などに使用されている多重巻きパイプの素材である銅めっき鋼板の製造方法に関する。 The present invention relates to a vibration of the car - Kichu - Bed to a method for producing a copper-plated steel sheet which is a material of the multi-turn pipe which is used like a refrigerator cooling tube.

【002】 [002]

【従来技術】銅めっき鋼板を用いての多重巻きパイプの製造は、所定幅に裁断した銅めっき鋼板を造管用ロ−ルでパイプ状に多重に巻き重ねた後、銅の融点以上(例えば、1150℃に加熱した窒素と水素の混合ガス雰囲気中)に2〜3分間保持して、銅めっき層を融着させ、その融着しためっき層で巻き重ね面間を相互に融着接合させる、いわゆるセルフブレ−ジングで行っている。 Production of multi-turn pipe of the prior art Using the copper plating steel sheet, forming pipe b copper plated steel sheet was cut to a predetermined width - after wound up into multiple pipe shape by Le, copper higher than the melting point (e.g., and held in a mixed gas atmosphere) of heated nitrogen and hydrogen 1150 ° C. 2 to 3 minutes, a copper plating layer are fused each other to fuse bonding between wound lap surface in the plating layer were the fused, the so-called Serufubure - is doing in managing. 図5 Figure 5
は、このような方法で製造した2重巻きパイプの断面を示すもので、1が冷延鋼板、2が銅めっき層、3がセルフブレ−ジングにより形成された銅融着層で、銅融着層による巻き重ね面間の接合性の良否は、渦電流探傷などの非破壊試験で調査している。 Is intended to indicate such a way a double-wound pipe section produced in, 1 is cold-rolled steel sheet, 2 copper plating layer, 3 is Serufubure - in DoToru adhesive layer formed by Zing, DoToruchaku bondability quality between wound lap surface by the layer is investigated in non-destructive testing, such as eddy current testing.

【003】この多重巻きパイプ製造に使用する銅めっき鋼板の製造方法としては、鋼板に脱脂、酸洗などの表面清浄化前処理を施した後、置換析出の起こらないシアン化銅めっき液にて下地電気銅めっきを0.1〜0.3μm [003] As a method for producing a copper-plated steel sheet for use in this multi-turn pipe production, degreasing the steel sheet, after being subjected to surface cleaning pretreatment such as pickling, with copper cyanide plating solution does not occur the displacement deposition 0.1~0.3μm an underlying copper electroplating
施し、その後硫酸銅めっき液にて厚付けの上層電気銅めっきを施す方法が開発されている(特公平1−3355 Subjected, after which the method of applying the upper layer copper plating thick layer with sulfuric acid copper plating solution has been developed (KOKOKU 1-3355
8号)。 No. 8).

【004】しかしながら、下地電気銅めっきをシアン化銅めっき液で行うと、めっき液は毒性が強いため、作業性が劣り、また、シアンイオン(CN - )が次に示す電解反応によりシアン酸イオン(CNO - )に酸化され、それがさらに加水分解により炭酸イオン(CO 3 2- )に分解されて、炭酸根として蓄積されてしまう。 [004] However, when the base copper electroplating with copper cyanide plating solution, since the plating solution strongly toxic, poor workability, and cyanide ion (CN -) cyanate ions by the following electrolysis reactions (CNO -) is oxidized in, it is further decomposed into carbonate ion (CO 3 2-) by hydrolysis, it would be stored as carbonate groups. CN - +2OH - =CNO - +H 2 O+2e - CNO - +2H 2 O=NH 4 + +CO 3 2- CN - + 2OH - = CNO - + H 2 O + 2e - CNO - + 2H 2 O = NH 4 + + CO 3 2-

【005】しかして、この炭酸根が蓄積されると、めっき液の寿命は短くなり、しかも、めっきの電流効率が大きく変動したりするものであった。 [005] Thus, when the carbonate groups are accumulated, the life of the plating solution is shortened, moreover, were those current efficiency of plating or vary greatly. このため、このような問題を避けるため、下地電気銅めっきをピロリン酸銅、このピロリン酸銅以外のピロリン酸塩およびシュウ酸塩からなるピロリン酸銅めっき液にて行っていた。 Therefore, to avoid such a problem, it has been performed an underlying copper plating copper pyrophosphate at pyrophosphate copper plating solution consisting of pyrophosphate and oxalic acid salts other than the copper pyrophosphate.

【006】 [006]

【発明が解決しようとする問題点】しかしながら、このめっき液で下地電気銅めっきを施して、工業的に多重巻きパイプ用銅めっき鋼板を製造すると、めっき液組成、 THE INVENTION Problems to be Solved] However, by applying the undercoat copper electroplating in this plating solution, when industrially producing a copper-plated steel sheet for multi-turn pipe, plating solution composition,
液温、電流密度、液流速などのめっき条件を一定にしても、多重巻きパイプ製造のセルフブレ−ジングの時に銅めっき層の一部が流れてなくなる銅垂れやボイド(融着欠陥部分)が発生し、一定の品質の製品が得られないものであった。 Liquid temperature, current density, even if the constant plating conditions such as the liquid flow rate, the multi-turn pipe manufacturing Serufubure - copper sag and voids (fused defect) eliminated a part of the copper plating layer flows when managing occurred and, it was those that can not be obtained certain of the quality of the product. 本発明は、このセルフブレ−ジングの時に発生する銅垂れやボイドの問題を解決した多重巻きパイプ用銅めっき鋼板の製造方法を提供するものである。 The present invention, this Serufubure - is to provide a method of manufacturing a multi-turn pipe copper coated steel sheet which has solved the copper sagging and voids problems that occur when the managing.

【007】 [007]

【問題点を解決するための手段】本発明は、下地電気銅めっきをピロリン酸銅、このピロリン酸銅以外のピロリン酸塩およびシュウ酸塩からなるピロリン酸銅めっき液を用いて施す際、めっき液中の鉛濃度を250ppm以下、アンチモンおよび錫の合計濃度を600ppm以下にして、銅垂れやボイドが発生しないようにした。 The present invention, in order to solve the problems] is copper pyrophosphate underlying copper electroplating, when performing with pyrophosphate copper plating solution consisting of pyrophosphate and oxalic acid salts other than the copper pyrophosphate plating hereinafter 250ppm lead concentration in the solution, and the total concentration of antimony and tin below 600 ppm, copper dripping and voids were not to occur.

【008】 [008]

【作用】本発明者らは、電気銅めっき鋼板を素材とする多重巻きパイプ製造の際に発生する銅垂れやボイドの原因を追及した結果、下地電気銅めっき液中の不純物元素である鉛、アンチモンおよび錫の濃度が関係し、これらの濃度がある程度以上高くなると、セルフブレ−ジングの際に銅垂れやボイドが発生することを見出だした。 SUMMARY OF] The present inventors, as a result of pursuing the cause of copper dripping and voids generated during the multi-turn pipe production for a material of copper-plated steel sheet, which is an impurity element of the underlying copper plating solution of lead, related concentrations of antimony and tin, if these concentrations higher than a certain, Serufubure - copper dripping or voids we have found to occur during GIN.

【009】また、本発明者らの調査によれば、鉛、アンチモン、錫の不純物元素の銅垂れやボイド発生に及ぼす影響は、同一濃度の場合、アンチモンや錫より鉛の方が大きく、元素により異なることが判明した。 [009] In addition, according to a study by the inventors of the present invention, lead, antimony, impact on the copper dripping or voids of impurity elements of tin, in the case of the same concentration, larger in the lead than antimony and tin, elements different it was found by.

【010】図1と図2は、下地電気銅めっき中の鉛含有量の異なる電気銅めっき鋼板を製造して、この鋼板を多重巻きパイプに加工した場合の下地電気銅めっき液中の鉛イオン濃度と銅垂れとの関係(図1)およびボイド発生との関係(図2)を示したものである。 [010] Figure 1 and Figure 2 are produced with different copper electroplating steel sheet lead content in the underlying electrolytic copper plating, lead ions of the underlying copper plating solution in the case of processing the steel sheet to multi-turn pipe It shows the relationship between the concentration and the copper drip relationship between (1) and voiding (Figure 2). なお、下地電気銅めっきは、ピロリン酸銅(Cu 227・3H 2 O)56 Note that the base copper electroplating, copper pyrophosphate (Cu 2 P 2 O 7 · 3H 2 O) 56
g/l、ピロリン酸カリウム(K 427 )253g/l、 g / l, potassium pyrophosphate (K 4 P 2 O 7) 253g / l,
pH8.7、P比(P 27 4- /Cu 2+ )8のピロリン酸銅めっき液中に鉛イオンを添加して、液温60℃、電流密度5A/dm 2の条件で鋼板に膜厚0.3μm施し、上層電気銅めっきは、硫酸銅200g/l、硫酸45g/lからなる硫酸銅めっき液を用いて、液温30℃、電流密度1 pH 8.7, was added to lead ions in a copper pyrophosphate plating solution in P ratio (P 2 O 7 4- / Cu 2+) 8, liquid temperature 60 ° C., the steel sheet at a current density of 5A / dm 2 thickness 0.3μm subjected, the upper copper electroplating, copper sulfate 200 g / l, using a copper sulfate plating solution comprising sulfuric acid 45 g / l, solution temperature 30 ° C., a current density of 1
5A/dm 2の条件で鋼板に膜厚3μm施した。 Steel plate subjected thickness 3μm to the condition of 5A / dm 2.

【011】図1、図2より明らかなように、下地電気銅めっき液中の鉛イオン濃度が250ppm以上になると、 [011] Figure 1, as is clear from FIG. 2, the lead ion concentration in the underlying electrolytic copper plating solution is more than 250 ppm,
銅垂れやボイドの発生率が急激に高くなる。 Copper dripping and void incidence of is rapidly increased.

【012】また、図3と図4は、上記ピロリン酸銅めっき液と同一組成のめっき液に鉛イオンの代わりに、アンチモン、錫の各イオンを添加して、前記めっき条件で膜厚0.3μmの下地電気銅めっきを施し、さらにその上に、前記上層電気銅めっきと同一めっき液、めっき条件で上層電気銅めっきを施して、電気銅めっき鋼板を製造し、この鋼板を用いて多重巻きパイプに加工した場合のアンチモン、錫の各イオン濃度と銅垂れとの関係(図3)およびボイド発生との関係(図4)を示したものであるが、銅垂れやボイドの発生は、アンチモン、錫の各イオンを個々に添加した場合でも、同時に添加した場合でも同様の傾向を示し、単独または合計イオン濃度が6 [012] Also, FIGS. 3 and 4, instead of lead ions in the plating solution of the same composition as the copper pyrophosphate plating solution, antimony, by adding each ion in the tin film thickness by the plating condition 0. performing underlying copper plating 3 [mu] m, further thereon, the upper layer copper plating in the same plating solution, subjected to the upper layer copper plating in the plating conditions, to produce a copper plated steel sheet, multi-turn using this steel plate antimony when processed into a pipe, but illustrates the relationship between each ion concentration and the copper drip tin (Figure 3) and the relationship between the voids (Fig. 4), the occurrence of copper sagging or voids, antimony even when adding each ion tin individually, it showed a similar tendency even when added simultaneously, either alone or in total ion concentration 6
00ppm以上になると、発生率が著しく高くなる。 It becomes more than 00ppm, significantly higher incidence.

【013】これらの不純物金属イオンがめっき液中に含まれると、銅垂れが発生するのは、下地電気銅めっきの際に銅とともに不純物金属イオンが共析して、融点の低い下地銅めっき層が形成され、セルフブレ−ジングの際この下地電気銅めっき層が上層電気銅めっき層より先に溶融してしまうためと考えられる。 [013] When these impurity metal ions contained in the plating solution, the copper dripping occurs, and impurity metal ions with copper eutectoid when the underlying copper electroplating, low base copper plating layer having a melting point There is formed, Serufubure - the underlying copper plating layer during GIN is considered for melts earlier than upper layer copper plating layer.

【014】また、ボイドが発生するのは、不純物金属イオンの共析により下地電気銅めっき層の残留応力が高くなることが原因と考えられる。 [014] Further, the voids are generated, it is considered a cause of the residual stress of the base copper plating layer by codeposition of the impurity metal ions is high. すなわち、下地電気銅めっき層の残留応力が存在すると、多重巻きパイプへの造管の際に多くのクラックが発生するため、この影響で上層電気銅めっき層にも多くのクラックが発生し、このクラック部分がセルフブレ−ジングの時に完全に融着しないためと考えられる。 That is, when the residual stress in the underlying copper plating layer is present, because many cracks during pipe formation to multi-turn pipe occurs, even many cracks occurred on the upper copper electroplating layer in this effect, the presumably because it not completely fused at GIN - crack portion Serufubure.

【015】ところで、鉛、アンチモン、錫の各イオンは、電気銅めっき鋼板製造の際、ピロリン酸銅めっき液中に通常共存するので、各金属イオンは、さらに厳しく管理するのが好ましい。 [015] Meanwhile, lead, antimony, each ion of tin, when copper electroplating steel sheet production, since normally coexist in a copper pyrophosphate plating solution, the metal ions are preferably managed more strictly.

【016】 [016]

【実施例】ピロリン酸銅(Cu 227・3H 2 O)56g/ EXAMPLES pyrophosphate (Cu 2 P 2 O 7 · 3H 2 O) 56g /
l、ピロリン酸カリウム(K 427 )253g/l、pH l, potassium pyrophosphate (K 4 P 2 O 7) 253g / l, pH
8.7、P比(P 27 4- /Cu 2+ )8からなるピロリン酸銅めっき液中に鉛、アンチモンおよび錫の各イオンを同時に添加して、添加金属イオンの異なるめっき液とし、このめっき液を用いて、液温60℃、電流密度5A/dm 2 8.7, was added lead pyrophosphate copper plating solution consisting of P ratio (P 2 O 7 4- / Cu 2+) 8, each ion of antimony and tin simultaneously, a different plating solution of the added metal ions using this plating solution, solution temperature 60 ° C., a current density of 5A / dm 2
の一定条件で鋼板に膜厚0.3μmの下地電気銅めっきを施し、さらにその上に、硫酸銅200g/l、硫酸4 Performing underlying copper electroplating having a thickness of 0.3μm on the steel sheet at a constant condition, further thereon, copper sulfate 200 g / l, 4 sulfate
5g/lからなる硫酸銅めっき液を用いて、液温30 Using sulfuric acid copper plating solution consisting of 5 g / l, solution temperature 30
℃、電流密度15A/dm 2の一定条件で上層電気銅めっきを膜厚3μm施した。 ° C., was subjected thickness 3μm the upper copper electroplating with a constant a current density of 15A / dm 2.

【017】以上のようにして製造した電気銅めっき鋼板より試験片を採取して、銅垂れ発生の有無調査およびボイド試験を行った。 [017] were taken from the test piece copper-plated steel sheet was prepared in the manner described above, it was carried out the presence or absence research and void test of copper sagging occur. 銅垂れ発生の有無は、100×10 The presence or absence of copper sagging occurs, 100 × 10
0mmの試験片を45度傾斜させた状態で窒素ガス雰囲気中で1120〜1130℃に5分間加熱して、銅めっき層の銅垂れ発生有無を調査した。 1120-1130 ° C. in a nitrogen gas atmosphere and heated for 5 minutes in a state of being inclined 0mm specimens 45 degrees, was investigated copper sag occurrence or non-occurrence of the copper plating layer. また、ボイド試験は、試験片を2枚重ね合わせたものを100個作成して、それらを窒素ガス雰囲気中で前記温度に3分間加熱することにより銅めっき層を融着させ、ボイド発生有無を渦電流で探傷する方法で行った。 Further, the void test creates 100 a a superposition two test pieces, they copper-plated layer fused by heating for 3 minutes in the temperature in a nitrogen gas atmosphere, the void occurrence or non-occurrence It was carried out in a way that flaw in the eddy current. この結果を第1表に示す。 The results are shown in Table 1.

【018】 [018]

【第1表】 [Table 1]

【019】 [019]

【発明の効果】以上のように、本発明の銅めっき鋼板の製造方法によれば、電気銅めっき鋼板を多重巻きパイプに加工した場合の下地電気銅めっきによる銅垂れやボイド発生を防止できる。 As is evident from the foregoing description, according to the manufacturing method of the copper-plated steel sheet of the present invention can prevent the copper dripping and voids caused by underlying copper electroplating in the case of processing a copper-plated steel sheet to multi-turn pipe.

【図面の簡単な説明】 BRIEF DESCRIPTION OF THE DRAWINGS

【図1】下地電気銅めっき用のピロリン酸銅めっき液中の鉛イオン濃度と、その鉛イオン含有めっき液で下地電気銅めっきを施して製造した銅めっき鋼板を多重巻きパイプに加工した場合の銅垂れ発生との関係を示すグラフである。 [1] in the case of machining with lead ion concentration in the copper pyrophosphate plating solution for undercoat electrolytic copper plating, copper plating steel sheet produced by subjecting a base copper electroplating with the lead ions contained plating solution multi-turn pipe it is a graph showing the relationship between the copper sag occurs.

【図2】下地電気銅めっき用のピロリン酸銅めっき液中の鉛イオン濃度と、その鉛イオン含有めっき液で下地電気銅めっきを施して製造した銅めっき鋼板を多重巻きパイプに加工した場合のボイド発生率との関係を示すグラフである。 [Figure 2] and the lead ion concentration in the copper pyrophosphate plating solution for undercoat electrolytic copper plating, in the case of processing a copper-plated steel sheet produced by subjecting a base copper electroplating with the lead ions contained plating solution multi-turn pipe is a graph showing the relationship between the void generation rate.

【図3】下地電気銅めっき用のピロリン酸銅めっき液中のアンチモンまたは錫のイオン濃度と、その各金属イオン含有めっき液で下地電気銅めっきを施して製造した銅めっき鋼板を多重巻きパイプに加工した場合の銅垂れ発生との関係を示すグラフである。 [3] and the ion concentration of antimony or tin in the underlying copper pyrophosphate plating solution for electrolytic copper plating, copper plating steel sheet produced by subjecting a base copper electroplating in that each metal ion-containing plating solution multi-turn pipe it is a graph showing the relationship between the copper sagging occurs in the case of machining.

【図4】下地電気銅めっき用のピロリン酸銅めっき液中のアンチモンまたは錫のイオン濃度と、その各金属イオン含有めっき液で下地電気銅めっきを施して製造した銅めっき鋼板を多重巻きパイプに加工した場合のボイド発生率との関係を示すグラフである。 [Figure 4] and the ion concentration of antimony or tin in the underlying copper pyrophosphate plating solution for electrolytic copper plating, copper plating steel sheet produced by subjecting a base copper electroplating in that each metal ion-containing plating solution multi-turn pipe it is a graph showing the relationship between the void generation rate when processed.

【図5】銅めっき鋼板を用いて製造した二重巻きパイプの断面図である。 5 is a cross-sectional view of a dual-winding pipe produced using the copper-plated steel plate.

【符号の説明】 DESCRIPTION OF SYMBOLS

1 冷延鋼板 2 銅めっき層 3 銅融着層 1 cold-rolled steel sheet 2 copper plated layer 3 DoToru sealable layer

───────────────────────────────────────────────────── フロントページの続き (72)発明者 渡辺 栄次 大阪府堺市石津西町5番地 日新製鋼株 式会社 鉄鋼研究所 表面処理研究部内 (58)調査した分野(Int.Cl. 6 ,DB名) C25D 3/38 C25D 5/00 - 7/12 ────────────────────────────────────────────────── ─── front page of the continuation (72) inventor Eiji Watanabe Sakai, Osaka Prefecture Ishizunishi-cho 5 address Nisshin steel Co., Ltd. Iron and steel Institute surface treatment research portion (58) investigated the field (Int.Cl. 6, DB name ) C25D 3/38 C25D 5/00 - 7/12

Claims (1)

    (57)【特許請求の範囲】 (57) [the claims]
  1. 【請求項1】 鋼板に前処理を施した後、下地電気銅めっきを施し、その後上層電気銅めっきを施す銅めっき鋼板の製造方法において、前記下地電気銅めっきをピロリン酸銅、このピロリン酸銅以外のピロリン酸塩およびシュウ酸塩からなるピロリン酸銅めっき液を用いて施す際、めっき液中の鉛濃度を250ppm以下、アンチモンおよび錫の合計濃度を600ppm以下にすることを特徴とする多重巻きパイプ用銅めっき鋼板の製造方法。 Was subjected to 1. A steel plate pretreatment, subjected to underlying copper plating, then the method for producing a copper-plated steel sheet subjected to the upper layer copper plating, copper pyrophosphate and the underlying copper plating, the copper pyrophosphate when performing with pyrophosphate copper plating solution consisting of pyrophosphate and oxalic acid salts other than the lead concentration in the plating solution 250ppm or less, multi-turn, which comprises a total concentration of antimony and tin in the following 600ppm method for producing a copper-plated steel pipes.
JP4265191A 1991-02-14 1991-02-14 Method for producing a copper-plated steel sheet for multi-turn pipe Expired - Lifetime JP2832758B2 (en)

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JP4265191A JP2832758B2 (en) 1991-02-14 1991-02-14 Method for producing a copper-plated steel sheet for multi-turn pipe

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Application Number Priority Date Filing Date Title
JP4265191A JP2832758B2 (en) 1991-02-14 1991-02-14 Method for producing a copper-plated steel sheet for multi-turn pipe

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JPH06108284A JPH06108284A (en) 1994-04-19
JP2832758B2 true JP2832758B2 (en) 1998-12-09

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Publication number Priority date Publication date Assignee Title
WO1999057342A1 (en) * 1998-04-30 1999-11-11 Ebara Corporation Method and device for plating substrate

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